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EP2174914A1 - Procédé de traitement du trioxyde de diarsenic - Google Patents

Procédé de traitement du trioxyde de diarsenic Download PDF

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Publication number
EP2174914A1
EP2174914A1 EP08791096A EP08791096A EP2174914A1 EP 2174914 A1 EP2174914 A1 EP 2174914A1 EP 08791096 A EP08791096 A EP 08791096A EP 08791096 A EP08791096 A EP 08791096A EP 2174914 A1 EP2174914 A1 EP 2174914A1
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Prior art keywords
arsenic
solution
copper
reaction
oxidation
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German (de)
English (en)
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EP2174914A4 (fr
Inventor
Mitsuo Abumiya
Yusuke Sato
Hironobu Mikami
Masami Oouchi
Tetsuo Fujita
Masayoshi Matsumoto
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Dowa Metals and Mining Co Ltd
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Dowa Metals and Mining Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G28/00—Compounds of arsenic
    • C01G28/005—Oxides; Hydroxides; Oxyacids
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method of processing diarsenic trioxide (As 2 O 3 ) and heavy metal; of extracting arsenic from diarsenic trioxide, and crystallizing it into a scorodite crystal which is a stable arsenic compound.
  • Patent Document 1 describes a method of producing scorodite directed to arsenic that is contained in smelter soot.
  • Patent Document 2 relates to a method of leaching arsenic sulfide. It describes adding alkali while blowing air to slurry that contains arsenic sulfide, and leaching arsenic while maintaining the pH to 5 to 8.
  • Non-Patent Document 1 reports solubility products of iron arsenate, calcium arsenate and magnesium arsenate. According to the document, while calcium arsenate and magnesium arsenate are stable only in an alkali region, iron arsenate is stable in a neutral to acidic region. The document reports the minimum solubility 20 mg/l at pH 3.2.
  • Non-Patent Document 2 discloses solubility of iron arsenate and scorodite. The document indicates that solubility of arsenic from scorodite in a weak acidic region is lower than solubility of arsenic from amorphous iron arsenate by two digits, which discloses that scorodite is a stable arsenic compound.
  • Non-Patent Document 3 describes a method of producing scorodite directed to arsenic that is contained in wastewater from sulfuric acid plants or smelters.
  • Patent document 1 Japanese Patent Application Laid Open No. 2005-161123
  • Patent document 2 Japanese Patent Publication No. 61-24329
  • Non-patent document 1 Tadahisa Nishimura, Kazumitsu Tozawa, "Report of Research Institute of Mineral Dressing and Metallurgy, Tohoku University" No. 764, Vol. 34, Separate Print No. 1, 1978, J une [Non-patent document 2] E. Krause and V. A.
  • examples of pollutions concerned in non-ferrous smelting are air pollution caused by SO 2 gas, and soil and wastewater pollutions caused by arsenic.
  • the content of arsenic in copper ore is expected to increase in the future, implementation of full-scale measures will be further required than ever.
  • coastal non-ferrous smelters in Japan have been conducting their operations without problems by using clean concentrates as treated materials.
  • the inventors thought that an art will be necessary of taking arsenic as smelting intermediates to the outside of the system, stabilizing it in a certain form, and controlling and storing it.
  • Patent documents or Non-Patent documents describe a method of processing diarsenic trioxide, which extracts arsenic from diarsenic trioxide or a non-ferrous smelting intermediate containing diarsenic trioxide, and converts it into a stable arsenic compound.
  • An object of the present invention is to provide a method of processing diarsenic trioxide; which extracts arsenic from diarsenic trioxide, and processes it to a scorodite crystal with good filterbility and stability.
  • arsenic can be recovered as scorodite with good filterbility and stability: by implementing a leaching step of adding water and an oxidant to diarsenic trioxide to leach arsenic in leachate; next, implementing a solution adjusting step of removing the oxidant remaining in the leachate so as to obtain an adjusted solution; and further implementing a crystallizing step of converting arsenic in the adjusted solution to a scorodite crystal.
  • an oxidation reaction of oxidizing trivalent arsenic to pentavalent arsenic in a short period of time can be performed by blowing an oxidized gas into an aqueous solution containing the trivalent arsenic while heating the aqueous solution containing the trivalent arsenic in the presence of the three types of substances that are copper sulfide, copper ions, and copper pentavalent arsenic compounds as catalysts.
  • the present inventors confirmed that 99% or more of the trivalent arsenic is oxidized to a pentavalent form at the stop of this oxidation reaction, and have thus achieved the present invention.
  • the first means to resolve the aforementioned problem is a method of processing diarsenic trioxide, including: a leaching step of adding water to diarsenic trioxide (As 2 O 3 ) to produce slurry, and leaching arsenic while heating the slurry and adding an oxidant to obtain leachate; a deoxidization step of removing an oxidant remaining in the leachate to obtain an adjusted solution; and a crystallizing step of converting arsenic in the adjusted solution to scorodite crystal.
  • the second means is the method of processing diarsenic trioxide according to claim 1, wherein the leaching step uses hydrogen peroxide as the oxidant.
  • the third means is the method of processing diarsenic trioxide according to the first means, wherein the leachate is brought into contact with the metallic copper and remaining hydrogen is removed in the deoxidization step.
  • the fourth means is the method of processing diarsenic trioxide according to any of the first to third means, wherein ferrous (Fe 2+ ) salt is added and dissolved in the adjusted solution and this ferrous salt is oxidized, thereby converting arsenic in the adjusted solution to scorodite crystal in the crystallizing step.
  • the fifth means is the method of processing diarsenic trioxide according to the fourth means, wherein one of air and oxygen gas or mixed gas thereof is blown to the adjusted solution to oxidize the ferrous salt.
  • the sixth means is the method of processing diarsenic trioxide according to any of the first to fifth means, wherein the crystallizing step is performed in a region where the pH is 1 or less.
  • the seventh means is the method of processing diarsenic trioxide according to any of the first to sixth means, wherein the crystallizing step is performed at 50°C or higher.
  • the eighth means is an arsenic oxidation method, wherein by blowing at least one of air and/or oxygen gas into a solution that contains at least one of diarsenic trioxide (As 2 O 3 ) and/or arsenous acid ions, is heated to 50°C or higher, has a pH of not less than 1 in a neutral region, and comprises copper sulfide, copper ions, and a copper pentavalent arsenic compound, trivalent arsenic in the solution is oxidized to pentavalent arsenic.
  • As 2 O 3 diarsenic trioxide
  • the nineth means is an arsenic oxidation method, wherein by blowing at least one of air and/or oxygen gas into a solution that contains at least one of diarsenic trioxide (As 2 O 3 ) and/or arsenous acid ions, is heated to 50°C or higher, has a pH of not less than 2 in a neutral region, and comprises copper sulfide, trivalent arsenic in the solution is oxidized to pentavalent arsenic, while generating the copper pentavalent arsenic compound by dissolving a portion of the copper sulfide.
  • As 2 O 3 diarsenic trioxide
  • the tenth means is the arsenic oxidation method according to the eighth or nineth means, wherein the pH is not less than 2 when the blowing of at least one of air and/or oxygen gas starts, and less than 2 when the blowing of at least one of air and/or oxygen gas ends.
  • the eleventh means is the arsenic oxidation method according to any of the eighth to eleventh means, wherein after the trivalent arsenic in the solution is oxidized to the pentavalent arsenic, the solution produced by pulp is filtered and a filtering residue is recovered, and the filtering residue is used as a substitute for the copper sulfide.
  • the twelfth means is the arsenic oxidation method according to any of the eighth to eleventh means, wherein after the trivalent arsenic in the solution is oxidized to the pentavalent arsenic, the solution produced by pulp is neutralized to bring the pH to not less than 3 and thereby crystallize the copper ions in the solution as the copper pentavalent arsenic compound, and then filtering is performed to recover a filtrate and a filtering residue, and the filtering residue is used as a substitute for the copper sulfide.
  • arsenic can be extracted from diarsenic trioxide, and processed to scorodite crystal with good filterbility and stability.
  • trivalent arsenic can be oxidized to pentavalent arsenic at an oxidation rate of 99% or more with low operation costs and low equipment costs, by using materials that are easily obtainable in non-ferrous smelters.
  • the pH of the solution at the stop of the oxidation reaction is not less than 1 and below 2, which is favorable for producing scorodite (FeAsO 4 ⁇ 2H 2 O). In this respect, too, the present invention contributes to low operation costs and low equipment costs.
  • the present invention relates to a method of processing diarsenic trioxide, including: a leaching step of obtaining leachate in which arsenic is leached while adding an oxidant to diarsenic trioxide; a solution adjusting step of removing the oxidant remaining in the leachate so as to obtain an adjusted solution; and a crystallizing step of converting arsenic in the adjusted solution to scorodite crystal.
  • the present invention also relates to a method of oxidizing trivalent arsenic to pentavalent arsenic at an oxidation rate of 99% or more with low operation costs and low equipment costs.
  • a first embodiment will be explained in details on 1. Diarsenic trioxide; 2.
  • Diarsenic trioxide (1) according to the present invention is recovered as an intermediate product in industries such as a non-ferrous smelter industry or the like.
  • use of the present processing method is not limited in smelters that discharge arsenic to the outside of the system as a non-ferrous smelting intermediate containing diarsenic trioxide in an existing smelting step. It is also effective for smelters in which arsenic is stored as diarsenic trioxide.
  • the leaching step (2) according to the present invention will now be explained.
  • water is added to diarsenic trioxide in solid power (1) to produce slurry, the slurry is heated, and arsenic is leached while adding an oxidant.
  • the amount of water to be added should be reduced.
  • the water may be industrial water, intermediate water in the treatment process or the like.
  • the oxidant should be preferably added after the slurry is produced, because this will make the reaction more stable. Normally, a small amount of the diarsenic trioxide dissolves in water as trivalent arsenic as shown below (Equation 1).
  • FIG. 2 shows solubility of diarsenic trioxide in water.
  • H 2 O 2HAsO 2 (Equation 1)
  • FIG. 2 is a graph with the vertical axis showing values of solubility of diarsenic trioxide and arsenic, and the horizontal axis showing the temperature.
  • solubility of arsenious acid in water is plotted as ⁇
  • solubility or arsenic in the aforementioned diarsenic trioxide is plotted as • at each temperature.
  • the arsenic concentration 40g/l or higher is required in the leachate (3).
  • the solution temperature need always be kept at 80°C or higher to obtain a trivalent arsenic solution having a concentration as high as 40g/l or higher.
  • an operation such as filtering or the like is required, and therefore, the solution temperature drops and arsenious acid is crystallized, which causes clog of filter fabric. Accordingly, a problem that the production is inoperable or the like occurs.
  • the method is to add water to diarsenic trioxide to produce slurry, heat it, and perform leaching while adding an oxidant to it.
  • the oxidation reaction from trivalent arsenic to pentavalent arsenic becomes is the rate-limiting reaction, trivalent arsenic in the solution is concentrated highly, whereby arsenic cannot be leached. Therefore, the present inventors have arrived an idea of using hydrogen peroxide as a preferable example of the oxidant. Use of hydrogen peroxide as the oxidant enables the oxidation reaction from trivalent arsenic to pentavalent arsenic to proceed in a short period of time.
  • Diarsenic trioxide and water in certain amounts are blended to produce a pulp.
  • the temperature of the pulp is increased to 50°C or higher, at which hydrogen peroxide is added. 10 to 15 minutes is enough for adding hydrogen peroxide.
  • the solution temperature will have reached approx. 80°C as described later.
  • stirring is maintained for 60 minutes or more in this state.
  • the reaction can be judged as completed at the time when the redox potential of the solution becomes 450 mV (Vs; Ag/AgCl) or less at 80°C.
  • the amount of hydrogen peroxide to be added may be the theoretical amount (i.e., 1 time equivalent) necessary for oxidation reaction of trivalent arsenic, when it is assumed that all arsenic contained in the pulp is trivalent arsenic.
  • the amount of hydrogen peroxide to be added is sometimes determined with use of the redox potential as a guideline. In this case, the amount is accpeptable as long as the redox potential after the addition is 500 mV or higher (Vs; Ag/AgCl) at 80 °C. Note that, commonly used hydrogen peroxide of concentration of 30 to 35% may be used.
  • the solution temperature should be preferably 50°C or higher. This temperature is preferable because this promotes dissolution of diarsenic trioxide in water and the oxidation reaction from dissolved trivalent arsenic to pentavalent arsenic. Note that, in the case where hydrogen peroxide is used as the oxidant, the oxidation reaction from trivalent arsenic to pentavalent arsenic caused by addition of hydrogen peroxide is the exothermic reaction. Accordingly, for example, in the case where a solution of an arsenic concentration as high as approx. 50g/l is to be prepared, when the solution temperature when addition of hydrogen peroxide is started is 60°C, the solution temperature when addition thereof in the certain amount will be approx. 80°C, although exothermic condition from the equipment is different.
  • the deoxidization step (4) is the step of removing the oxidant remaining in the leachate (3).
  • the oxidant that remains after the reaction oxidizes a part of ferrous (Fe 2+ ) which is added in the crystallizing step (5) which is the next step. Accordingly, it is preferable to remove the oxidant to accurately control the ferrous ion concentration.
  • a method of adding metallic colloid such as gold, silver, or the like and dissolving it is also conceivable in order to remove hydrogen peroxide that remains in the leachate (3). However, taking into consideration its handling property or generation of loss, the method is not appropriate in the actual operation.
  • the present inventors have achieved the mechanism of removing the remaining oxidant (for example, hydrogen peroxide) by consuming the oxidant rather than by degrading it.
  • the oxidant is brought into contact with the oxidized agent (for example, metallic cupper) and removed by being consumed as shown in (Equation 4).
  • the reaction temperature is preferably 40°C or higher to complete the reaction.
  • the reaction can be judged as completed at the time when the pH shows a constant value.
  • the crystallizing step (5) is a step of crystallizing pentavalent arsenic in the adjusted solution which is obtained in the deoxidization step (4) into scorodite (6).
  • the adjusted solution obtained after the deoxidization step (4) is preferably a highly-concentrated solution of arsenic concentration 20g/l or higher, and more preferably of 30g/l or higher.
  • ferrous sulfate is preferable from the perspective of corrosion resistance of the equipment and easiness of availability.
  • the additive amount of ferrous salt is 1 time equivalent or more of the number of moles of arsenic to be processed as iron purity, and preferably 1.5 times equivalent or more.
  • the temperature of the adjusted solution is increased to a predetermined reaction temperature.
  • the reaction temperature is preferably set to 90 to 100°C from the perspective of making the reaction under ambient atmosphere possible.
  • the pH, the arsenic concentration and the Fe concentration sharply dropped within 2 to 3 hours after the oxidation reaction at a high temperature started.
  • the indicated redox potential of the solution is 400 mV or higher (Vs; Ag/AgCl) at 95°C.
  • 90% or more of the arsenic contained is a crystal of scorodite (6).
  • the oxidation reaction at a high temperature is preferably continued for 5 to 7 hours to end the oxidation reaction at a high temperature in the complete equilibrium condition.
  • the aforementioned crystallizing step (5) allows easy reaction operation and can convert the contained arsenic into scorodite (6) crystal without the need of adjusting pH in the middle of the reaction.
  • a filtrate (9) that is generated may be treated by a wastewater treatment step (10).
  • the obtained scorodite (6) crystal is excellent in sedimentability and filterability, and achieves volume reduction with adhesive moisture approximately 10% after filtering and high arsenic grade as much as 30%.
  • the crystal is excellent in elution resistance and stability. Therefore, it is possible to remove arsenic in a stable form from the smelting step and store it.
  • the amount of hydrogen peroxide having a concentration as high as 30% is 65.7 g.
  • the time for adding hydrogen peroxide was set as 12 minutes.
  • the temperature at the stop of addition was adjusted to 80°C.
  • stirring was maintained at 80°C for 90 minutes to complete the reaction.
  • the leachate was recovered by suction filtration with use of filter paper No. 5C.
  • the grade of the recovered leachate is shown in Table 2.
  • arsenic is pentavalent arsenic.
  • the transitions of the temperature, the pH and the redox potential during the reaction are shown in Table 3. Note that the redox potential is Ag/AgCl reference value.
  • a powdery metallic copper of reagent grade 1 was prepared as deoxidant. 2.5 g of a powdery metallic copper was added to the obtained leachate, and the deoxidization step was performed at the reaction temperature 40 °C to obtain an adjusted solution. Table 4 shows the transition of the reaction. Note that the redox potential is Ag/AgCl reference value.
  • the obtained adjusted solution was diluted with pure water, and the arsenic concentration was adjusted to 45 g/l.
  • the solution 800 cc was transferred to a 2 L beaker, and its pH was adjusted to 1.15 by adding 95% sulfuric acid.
  • the above oxidation method using hydrogen peroxide achieves approximately 100% oxidation of trivalent arsenic by accelerating the trivalent arsenic oxidation speed and causing the reaction at a high solution temperature.
  • hydrogen peroxide is an expensive agent.
  • the oxidation method using ozone achieves approximately 100% oxidation of trivalent arsenic in a short period of time, irrespective of solution temperature.
  • this oxidation method has the following problems. Ozone generating equipment itself requires high costs. Furthermore, ozone has strong oxidizing power, so that the specification of peripheral apparatuses needs to be upgraded. This results in extremely high costs for the system as a whole. Because ozone is hazardous to humans, an ancillary facility for collecting and detoxifying ozone that is released to the atmosphere without reaction is necessary. Ozone is easy to dissolve in water than oxygen gas, and the solution after reaction has a peculiar pungent odor. To resolve this problem, a process of removing dissolved ozone in a subsequent step is necessary.
  • trivalent arsenic can be oxidized to pentavalent arsenic at an oxidation rate of 99% or more with low operation costs and low equipment costs, by using materials that are easily obtainable in non-ferrous smelters.
  • This embodiment is an optimum processing method for producing a highly concentrated arsenic solution.
  • trivalent arsenic of low solubility can be easily oxidized to pentavalent arsenic of high solubility. Therefore, by using diarsenic trioxide ⁇ 1> which is solid as the trivalent arsenic source, the diarsenic trioxide dissolves simultaneously with the oxidation of trivalent arsenic to pentavalent arsenic, which ensures the timely supply of trivalent arsenic.
  • a pentavalent arsenic solution of a concentration as high as several tens of g/L, that is, a concentrated arsenic acid solution can be easily produced.
  • the present inventors investigated the step of oxidizing trivalent arsenic by oxygen gas, using copper as an oxidation catalyst for arsenic.
  • Copper sulfide solid, copper sulfide powder, and the like can be used as the copper sulfide source ⁇ 2>. Furthermore, the powdery state is preferable from the perspective of ensuring reactivity.
  • copper sulfide can be mainly classified into the two compositions of CuS and Cu 2 S (there is also Cu 9 S 5 being a composition in which a portion of copper in crystal lattice is defective). In this embodiment, any of them is effective, and a mixture of them is also possible.
  • the copper sulfide source is preferably as pure copper sulfide as possible (copper sulfide of high purity with minimum impurities).
  • the copper sulfide recovered as smelting intermediates is used as the copper sulfide source ⁇ 2>.
  • the recovered copper sulfide contains substantial amounts of the aforementioned As 2 S 3 , ZnS, PbS, CdS, and the like. Therefore, it is not preferable to use the copper sulfide recovered as smelting intermediates directly as the copper sulfide source ⁇ 2>.
  • the recovered copper sulfide can be used if the aforementioned sulfides are removed beforehand by decomposition reaction or the like to thereby increase the purity as copper sulfide.
  • copper smelters copper sulfide of high purity suitable for the present invention can be easily produced according to the following method.
  • a substance that becomes copper ions in the solution to be treated can be used as the copper ion source ⁇ 3>.
  • copper sulfide is preferable, as it is solid at ordinary temperatures, but dissolves into water and immediately becomes copper ions.
  • metallic copper or metallic copper powder can also be used, it is necessary to wait for the dissolution until they are ionized.
  • Copper arsenate is available as the copper pentavalent arsenic compound according to the present invention. Copper arsenate has a solubility product comparable to iron arsenate (FeAsO 4 ), and is a pentavalent arsenic compound that is easily formed in the weakly acidic to neutral region. In this embodiment, copper sulfide is added to the solution containing trivalent arsenic with the initial pH value being set to 2 or more, and the oxidation reaction is started.
  • the oxidation of the trivalent arsenic to pentavalent arsenic and the supply of copper ions by the dissolution of the copper sulfide occur simultaneously on the surface of the added copper sulfide, and therefore the generation of copper arsenate is though to occur instantaneously.
  • the solution is naturally transferred to the weakly acidic region.
  • the pentavalent arsenic and the copper ions are both concentrated to the order of g/L. Due to this concentration, the generative capacity of the copper arsenate will not decrease.
  • the pH of the solution sinks below 1 into the acidic state, the forming capacity of the copper arsenate will not decrease significantly. Accordingly, it is preferable to control the pH.
  • the oxidation of arsenic is preferably performed at a higher solution temperature. Specifically, a temperature of 50°C or more is required for the progress of the oxidation of arsenic.
  • the solution is heated ⁇ 5> to 70 to 90°C and preferably about 80°C, in consideration of real operation and based on the premise such as the material of the reaction tank and the filtering operation after the reaction.
  • the oxidation reaction of trivalent arsenic is possible even when the blowing gas ⁇ 6> is air.
  • oxygen gas or a gas mixture of air and oxygen gas is used as the blowing gas ⁇ 6>, the oxidation speed is maintained even in the range where the arsenic concentration in the solution is low, and the blowing (gas) capacity decreases. As a result, heat loss associated with this is reduced, and the maintenance of the reaction temperature becomes easier. Therefore, it is preferable to use oxygen gas or a gas mixture of oxygen gas and air as the blowing gas ⁇ 6>, in terms of the oxidation speed and the reaction temperature maintenance.
  • blowing amount per unit time of the blowing gas ⁇ 6> its optimum value changes depending on the gas-liquid mixing state in the reaction tank. For example, by using a microscopic bubble generation apparatus and the like, the oxidation efficiency can be further improved, and the blowing amount can be reduced. Therefore, at the time of real operation, it is important to find the optimum value in consideration of the gas-liquid mixing state, the oxygen gas blowing method, and the like.
  • a basic equation of the oxidation reaction of trivalent arsenic according to the present invention is thought to be the following.
  • AS 2 O 3 + H 2 O 2HAsO 2 (Equation 15) Reaction in which diarsenic trioxide dissolves in water as arsenous acid (trivalent arsenic).
  • 2HAsO 2 + O 2 + 2H 2 O 2H 2 AsO 4 - + 2H + (Equation 16) Reaction in which arsenous acid (trivalent arsenic) oxides.
  • 2HAsO 2 + O 2 + 2H 2 O 2H 3 AsO 4 (Equation 17) Reaction in which arsenous acid (trivalent arsenic) oxides.
  • the efficient oxidation of trivalent arsenic and the control of the pH at the stop of the reaction to the weakly acidic state according to the present invention can be achieved by setting the pH at the beginning of the oxidation reaction (when the air and/or oxygen gas blowing starts) to 2 or more.
  • the pH of trivalent arsenate at the stop of the oxidation reaction was below 2 and more specifically about 1.8 in all cases, as shown by the results of Examples 5 to 9 described later.
  • the pentavalent arsenic solution whose pH is about 1 is used as the stock solution, and therefore the pH can be adjusted by adding a small amount of inverse neutralizing agent (for example, sulfuric acid).
  • inverse neutralizing agent for example, sulfuric acid
  • the pH at the stop of the reaction is preferably not less than 1 and below 2, though the details will be described in Example 6 below.
  • the product obtained in the above oxidation step ⁇ 4> is separated in the filtering ⁇ 7> into the filtrate ⁇ 8> and the filtrand ⁇ 9>.
  • an ordinary filtering method such as filter press can be applied. This is because, though a copper pentavalent arsenic compound is generated in teh above oxidation step ⁇ 4>, there is no problem of filterbility such as increased viscosity.
  • the obtained filtrate ⁇ 7> is an arsenate solution having a pH of about 1.8 as mentioned above. Since the pH of about 1.8 is preferable for producing pentavalent arsenic compounds, a pentavalen arsenic compound can be produced from the filtrate ⁇ 7> with low costs and high productivity.
  • the filtrand ⁇ 9> is a mixture of copper sulfide and a copper pendavalent arsenic compound, and accordingly can be repeatedly used as it is as an oxidation catalyst. When repeatedly using this, the catalyst effect can be expected to increase by newly adding copper sulfide of an amount equivalent to partially dissolved copper sulfide.
  • the ternary catalyst made up of copper sulfide, copper ions, and a copper pentavalent arsenic compound according to the present invention has both a high oxidation rate and a high oxidation speed.
  • the oxidation catalyst effects exhibited by this ternary catalyst is thought to be derived from the battery-like reaction caused by the contact of each type of ionson the copper sulfide surface.
  • Equation 23 shows the crystallization of CuS which is copper sulfide, and indicates that the CuS crystallization is ensured on the copper sulfide surface as the newly-formed surface of high activity.
  • Diarsenic trioxide of reagent grade (the grade is shown in Table 6) and copper sulfide of reagent grade (the grade is shown in Table 7) were prepared.
  • copper sulfide can be mainly classified into the two forms of CuS and Cu 2 S, and there is also a composition Cu 9 S 5 in which a portion of copper in crystal lattice is defective. Any of these forms is usable, and a mixture of these forms is applicable too.
  • the results of X-ray diffraction of copper sulfide used in this Example are shown in Fig. 4 . Note, in Fig.
  • the peak of CuS is plotted as ⁇
  • the peak of Cu 2 S is plotted as *
  • the peak of Cu 9 S 5 is plotted as ⁇ .
  • a 1 L beaker was used as the reaction vessel, a 2-stage turbine blade and 4 baffle plates of 700 rpm were used as the mixture device, and the gas blowing was conducted by blowing in oxygen gas using a glass tube from the bottom of the beaker (the oxidation was performed in a gas and liquid mixture in vigorous mixing).
  • the solution mixture and the oxygen gas blowing were continued for 90 minutes to oxidize the trivalent arsenic.
  • the temperature, pH, redox potential, copper ion amount, trivalent arsenic amount, and pentavalent arsenic amount of the solution were measured every 30 minutes. The measurement results are shown in Table 8. Note, the redox potential is Ag/AgCl reference electrode value.
  • Example 2 The same operations and measurements as in Example 2 were performed except that the amount of copper sulfide introduced in the reaction vessel was 24 g which is one half. Note, the pH of the solution immediately before the oxygen gas blowing start was 2.96 (at 80°C). The results of measuring the temperature, pH, redox potential, copper ion amount, trivalent arsenic amount, and pentavalent arsenic amount of the solution every 30 minutes are shown in Table 10, and the analysis results of the grade of the catalyst recovered as the residue and washed with water are shown in Table 11.
  • Example 3 the CuS additive amount is reduced by half of Example 2, to examine the effects of this reduction by half.
  • the oxidation speed of trivalent arsenic decreased a little when compared with Example 2, but the oxidation capacity was sufficiently maintained, and the oxidation of 99% or more was observed at the point of 120 minutes after the oxidation reaction start.
  • the oxidation capacity and speed of trivalent arsenic can both be considered favorable for practical use.
  • This Example is similar to Example 2, but further 16 g of copper sulfide of reagent grade (CuSO 4 ⁇ 5H 2 O) was introduced into the reaction vessel.
  • the amount of copper sulfide introduced is equivalent to 5 g/L as copper ions.
  • This Example relates to the case of increasing the copper ion concentration than in the initial stage of the reaction. Note, the pH of the solution immediately before the oxygen gas blowing start was 2.98 (at 80°C). The results of measuring the temperature, pH, redox potential, copper ion amount, trivalent arsenic amount, and pentavalent arsenic amount of the solution every 30 minutes are shown in Table 12.
  • the oxygen gas blowing was stopped at 120 minutes when the reaction ended.
  • the additive amount of the NaOH solution was 40 cc.
  • the total arsenic concentration in the filtrate obtained as a result of the filtering operation was 29.6 g/L, while the copper concentration was 80 mg/L.
  • the concentration decrease associated with the formation of the copper arsenate compound was observed.
  • the residue recovered as a result of the filtering operation was 165 g ⁇ wet.
  • Example 4 increases the Cu ion concentration than in the initial stage of the reaction in Example 2. From the results of Table 12, it can be understood that the reaction was complete at a high oxidation rate in Example 4, too. On the other hand, in Example 4, the oxidation speed decreased a little when compared with Example 2. This indicates that the copper ion concentration in the reaction system need not increased more than necessary. It can be judged that the sufficient copper ion concentration in the reaction system is approximately 1 to 5 g/L.
  • this Example recovers added copper ions as a copper pentavalent arsenic compound by neutralization.
  • the method of recovering copper ions is not limited to the method of recovering as a copper pentavalent arsenic compound, and may instead be a method of adding an agent that reacts with copper ions and forms copper sulfide, such as monatomic sulfur or ZnS.
  • Example 4 50 g of diarsenic trioxide of reagent grade was prepared.
  • the whole residue recovered in Example 4 (except 10 g ⁇ wet used for the measurement sample in Example 4) and 50 g of diarsenic trioxide were introduced into the reaction vessel, and 707 cc of pure water was added to repulp, to bring the moisture content in the pulp to be 800 cc.
  • This pulp was heated to 80°C, and then oxygen gas was started to be blown in from the bottom of the reaction vessel at 400 cc/min. Note, the pH of the solution immediately before the oxygen gas blowing start was 3.03 (at 79°C).
  • This Example 5 exhibited highest oxidation efficiency and a highest oxidation speed of Examples 2 to 6. Specifically, the oxidation of 95% was already observed at the point of 60 minutes from the reaction, and the oxidation rate of 99.6% which is approximately 100% was observed at the point of 90 minutes from the reaction.
  • the catalyst according to this Example 5 is the ternate catalyst of copper sulfide, copper ions, and a copper arsenate compound (copper pentavalent arsenic compound), too.
  • the catalyst according to this Example 5 especially has a high content ratio of the copper arsenate compound (copper pentavalent arsenic compound) compare to Example 2 and Example 3. This high content ratio of the copper arsenate compound is thought to contribute to the improved oxidation performance. In other words, this contribution phenomenon demonstrates that the formation and presence of the copper arsenate compound relates to the generation of the newly-formed surface of CuS of high activity.
  • Example 3 The same operations as in Example 3 were performed except that the pH immediately before the oxygen gas blowing start was adjusted to 1.0 (at 80 °C) by adding concentrated sulfuric acid to the pulp.
  • Example 6 is similar to Example 3 in the amount of copper sulfide added, but the pH of the solution immediately before the oxidation start was adjusted to 1. As a result, the oxidation capacity decreased when compared with Example 3, and the oxidation rate was 72% at the point of 120 minutes. Though the reaction needs to be performed for a long period of time to reach the oxidation rate of 100%, the oxidation capacity itself is sufficient.
  • the reason of the above oxidation speed decrease can be attributed to the fact that the coexisting copper sulfide was significantly reduced. Furthermore, when the pH of the solution is 1, the amount of dissolution of copper sulfide increases, so that the amount of copper sulfide recovered without dissolving (amount of recycle) decreases, which is disadvantageous in terms of cost, too. In view of the above, it is thought to be preferable to start the reaction by setting the pH of the solution to not less than 2 and ending the oxidation reaction with a pH of not less than 1, in terms of ensuring the reactivity and the CuS recovery amount.
  • Example 2 The same operation as in Example 2 was performed except that 50 g of diarsenic trioxide of reagent grade alone was introduced in the reaction vessel and 800 cc of pure water was added to repulp. Note, the pH of the solution immediately before the oxygen gas blowing start was 2.80 (at 80°C). The temperature, pH, redox potential, copper ion amount, trivalent arsenic amount, and pentavalent arsenic amount of the solution were measured every 30 minutes. The measurement results are shown in Table 18.
  • Example 2 The same operation as in Example 2 was performed except that 50 g of diarsenic trioxide of reagent grade and 16 g of copper sulfide of reagent grade (CuSO 4 ⁇ 5H 2 O) were introduced in the reaction vessel and 800 cc of pure water was added to repulp. Note, the pH of the solution immediately before the oxygen gas blowing start was 3.33 (at 80°C). The temperature, pH, redox potential, copper ion amount, trivalent arsenic amount, and pentavalent arsenic amount of the solution were measured every 30 minutes. The measurement results are shown in Table 19.
  • Example 2 The same operation as in Example 2 was performed except that 50 g of diarsenic trioxide of reagent grade and 32 g of copper sulfide of reagent grade (CuSO 4 ⁇ 5H 2 O) (10 g/L as copper ions) were introduced in the reaction vessel and 800 cc of pure water was added to repulp. Note, the pH of the solution immediately before the oxygen gas blowing start was 3.45 (at 80°C). The temperature, pH, redox potential, copper ion amount, trivalent arsenic amount, and pentavalent arsenic amount of the solution were measured every 30 minutes. The measurement results are shown in Table 20.
  • Example 2 The same operation as in Example 2 was performed except that 50 g of diarsenic trioxide of reagent grade, 48 g of copper sulfide of reagent grade (CuS), and 20 g of sulfur powder were introduced in the reaction vessel and 800 cc of pure water was added to repulp. Note, the pH of the solution immediately before the oxygen gas blowing start was 2.67 (at 80°C). The temperature, pH, redox potential, copper ion amount, trivalent arsenic amount, and pentavalent arsenic amount of the solution were measured every 30 minutes. The measurement results are shown in Table 21.
  • Example 2 The same operation as in Example 2 was performed except that concentrated sulfuric acid was added to pulp, the pH was adjusted to 0 (at 80°C), and then the oxygen gas blowing was started. The temperature, pH, redox potential, copper ion amount, trivalent arsenic amount, and pentavalent arsenic amount of the solution were measured every 30 minutes. The measurement results are shown in Table 23.
  • Comparative Example 5 indicate that, when starting the arsenic oxidation reaction under a condition where the pH is 0 which does not allow formation of copper sulfide, the substances that serve as catalysts are the binary system of copper sulfide and copper ions, which results in a significant drop of the oxidation capacity.
  • the arsenic oxidation reaction according to the present invention is preferably started under a condition where the pH is not less than 1.

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